Moving towards commercialization of lignocellulosic biomass to fuels to chemicals. How to deal with heterogeneous biomass?

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Moving towards commercialization of lignocellulosic biomass to fuels to chemicals. How to deal with heterogeneous biomass? Renata Bura, Shannon Ewanick, Erik Budsberg, Jordan Crawford, Brian Marquardt and Rick Gustafson November 13 th, 2012

Heterogeneous biomass Hybrid poplar Forest residues

How to deal with heterogeneous biomass?

Objectives How Objectives can we improve the production of fuels and chemicals from biomass? How do deal with heterogeneous lignocellulosic biomass? Preconditioning Online reaction control Techno-economical analysis Life Cycle Analysis (LCA)

Objectives How Objectives can we improve the production of fuels and chemicals from biomass? How do deal with heterogeneous lignocellulosic biomass? Preconditioning Online reaction control Techno-economical analysis Life Cycle Analysis (LCA)

Chemical composition of hybrid poplar Biomass Cellulose (%) Hemicellulose (%) Lignin (%) P. deltoides, Stoneville 42.2 16.6 25.6 NM 6 49.0 21.7 23.3 CAFI high lignin 43.8 20.4 29.1 CAFI low lignin 45.1 21.5 21.4 Caudina DN 34 43.7 19.6 27.2 DN 182 45.5 20.8 23.6 DN 17 43.7 23.2 23.1 NC 5260 45.1 20.3 21.5 (Sannigrahi et al., 2009)

Chemical composition-challenges Agronomy practices for stand establishment Water and nutrients management Weed control Harvest and storage Growing seasonal precipitation requirements Seasonal changes Age

Physical characteristics Moisture content Particle size Bark content Leaf/needle content Harvest and collection Storage Transportation Handling

Affect of preconditioning Biomass preconditioning Biomass treatment $ Product recovery and characteristics Pretreatment Cellulose conversion to glucose Hydrolysis Ethanol yield Pretreatment $$ Fermentation and SSF Enzyme $$$ Microorganism $$$ Ethanol

Switchgrass and sugarcane bagasse preparation Steam explosion Air-dry (10 % moisture) No SO 2 added 195-205 C 7.5-10 min Switchgrass Sugarcane bagasse (Hawaii) Soak to 80% moisture Add 3% SO 2 SO 2 Starting material Moisture adjustment SO 2 addition Pretreatment (Ewanick & Bura 2011)

Fermentation Biomass preconditioning Product recovery and quality Pretreatment steam explosion Cellulose conversion to glucose Hydrolysis 5% (w/w) 10 FPU/g Ethanol yield Fermentation SSF Ethanol

Ethanol % of theoretical Ethanol % of theoretical SSF 5% (w/w), 10 FPU/g cellulose, 5 g/l of S. cerevisiae Switchgrass Sugarcane bagasse 75 75 18% 60 20% 60 45 45 30 30 SG HM+SO 2 SCB HM+SO 2 15 0 0 4 8 12 16 20 24 28 32 Time (hours) SG LM+SO 2 SG HM SG LM 15 0 0 4 8 12 16 20 24 28 32 Time (hours) SCB LM+SO 2 SCB HM SCB LM (Ewanick and Bura, 2011; Bioresource Technology 102)

Final results theoretical ethanol yield from raw biomass Switchgrass - uncat Switchgrass Soaked Unsoaked Bagasse Bagasse - uncat Switchgrass - SO2 Switchgrass+SO 2 28% Bagasse+SO 2 Bagasse - SO2 28% 0% 0 20% 40% 60% 80% Theoretical ethanol yield from raw biomass (%) % of theoretical yield from raw biomass (Ewanick and Bura, 2011; Bioresource Technology 102)

How to deal with heterogeneous biomass? Pretreatment Hydrolysis Fermentation

Absorbance Improving analytical methods Current Spectroscopic 1.0 0.9 0.8 0.7 0.6 Methods 0.5 0.4 0.3 0.2 0.1 HPLC, GC, wet chemistry, enzymatic 1400 1200 Wavenumbers (cm-1) Raman High resolution chemical modification from molecular vibration 1000 800 600 Issues -time and cost -not online -less robust -requires trained personnel -destructive and invasive -background fluorescence -resolution of multiple compounds -detection limits

What is so special about UW Raman? Raman Instrument Kaiser Rxn2 System 785 nm excitation 6 mm ball probe (UW patent) Sapphire spherical lens Interfacial measurements No moving parts Sampling error <<1% Temperature range: -40 C 350 C Pressure range: 0-350 Barr Effective sampling of liquids, slurries, powders, pastes and solids Chemometric techniques (UW) Algorithms to remove fluorescence (UW)

Experimental methods Fermentation in 1.3 L NBS Bioflo 115 bioreactor S. cerevisiae ATCC 96581 (6-C only) 785 nm Raman ball probe in vessel Manual sampling for HPLC analysis Synthetic 30 g/l glucose 15 g/l xylose Switchgrass hydrolysate Steam exploded switchgrass + SO 2 Spiked w/ 30 g/l glucose

Intensity (Arb. Units) I n t e n s i t y Intensity (Arb. Units) ( A r b. 8 0 0 U n i t s ) R a m a n S h i f t ( c m - 1 ) 9 0 0 10 00 11 00 S a m p l e Raman: surface plots Synthetic sugars Switchgrass hydrolysate Ethanol Ethanol 800 1000 Raman Shift (cm -1 ) Glucose 1150 Time Glucose Raman Shift (cm -1 ) Time

HPLC vs Raman HPLC Raman 20000 15000 10000 5000 0 400 600 800 1000 1200 1400 1600 Sample preparation $$$ $ Equipment cost $$$ $$$ Sample run time 30-120 min 1 min Analysis time for 6 hour fermentation 3 days, 36 data points Real time, 360 data points Online probe/sensor? No Yes

Techno-economical analysis (ASPEN)

Life Cycle Analysis (LCA)

How to deal with heterogeneous biomass? 1. Preconditioning 2. Online reaction control 3. Techno-economical analysis 4. Life Cycle Analysis (LCA)

Acknowledgements Centre for Process Control and Analysis (CPAC) Novozymes Inc. Weyerhaeuser Inc. UW Applied Physics Laboratory Denman Professor in Bioresource Science Engineering Biofuels and Bioproducts Laboratory Research Group (www.depts.washington.edu/sfrbbl/)